Am.  J  our.  Pharm.  ] 
August,  1882.  j 
Methyl  Ethers  of  Morphine. 
413: 
consequence  of  the  recent  remarks  of  Dott  upon  the  same  subject,  I 
wish  as  a  supplement  to  that  communication  to  mention  some  facts  that 
I  have  observed  since  my  former  publication  on  the  ether  in  question. 
With  respect  first  to  the  «-ether,  it  is  known  that  it  differs  from 
codeine  only  slightly  in  its  optical  behavior.  It  turns  out,  however^ 
that  this  difference  is  not  an  essential  one,  since  the  hydrochlorate,  after 
several  recrystallizations  from  water,  agrees  perfectly  with  codeine 
hydrochlorate  in  its  optical  character  also.  There  is,  therefore,  no 
doubt  that  the  synthetically  prepared  codeine  is  identical  with  that 
occurring  in  opium. 
Experiments  which  were  made  by  me  to  clear  up  the  question 
showed  further  that  codeine,  or  the  «-methy}-ether  of  morphine^  is  also 
formed  when  morphine-potassium  is  used  (instead  of  morphine  sodium), 
but  that  the  yield  of  codeine  sometimes  amounts  to  not  more  than 
traces.  This  unfavorable  result  is  for  the  most  part  due  to  the  fact 
that  methyl  iodide  which  has  not  yet  taken  part  in  the  reaction,  com- 
bines with  the  codeine  formed  to  produce  iodoniethyl-codeine.  In  this 
process  there  is  also  a  formation  of  iodomethyl-morphine,,  and  when 
calculated  quantities  of  morphine,  methyl  iodide,  and  potassium 
hydrate  (or  sodium  hydrate)  are  used,  it  is  clear  that  at  the  conclusion 
of  the  reaction  free  alkali  must  be  present  in  the  solution. 
This  alkali  leaves  the  codeine  that  may  have  been  formed,  as  well 
as  the  iodomethyl-morphine,  unaltered  upon  warming,  but  the  iodo- 
methyl  codeine  very  readily  decomposes  it  in  accordance  with  the- 
equation : 
CVH,8(CH3)N03,CH3l + KOH= Ci/H,XCH3)2N03 + KT + H^O. 
Consequently  dimethylmorphine  is  formed,  and  it  was  this  body  that 
I  obtained  before  and  described  under  the  name  of  /9-methyl-mor- 
phine."    The  formation  of  this  body  takes  place  more  readily  when,^ 
as  was  done  by  me  previously,  alkali  is  added  before  extraction  with  . 
ether. 
The  /9-methyl-ether  is  naturally  most  conveniently  prepared  by  the 
direct  action  of  potash  soda  ley,  ammonia  or  baryta  water  upon  iodo- 
methyl-codeine.  Its  formation  takes  place  gradually  even  at  the  ordi- 
nary temperature,  but  rapidly  upon  heat  being  applied. 
r  had  on  a  former  occasion  found  the  amount  of  chh^rine  in  the 
hydrochlorate  somewhat  too  high,  whicli  would  on  the  other  hand 
account  for  a  deficiency  in  the  amount  of  carbon.  Th(^  ground  of  this 
fc^rmer  discrepancy  I  cannot  state^  sin«e  I  cannot  detect  any  contami- 
